Homogeneous flaked catalyst composition and its preparation



Patented July 29,1947

Lilli-l7ED-v PAT EN 7 OFF 4 2,424,811 I HQMOGENE U FL nQa i-icsa coi B I ON A D BRErAEAf-HQ Meyer Ii. Freed; Ansonia, Gonna, assignorto The Seymour Manufacturing Go, Seymour, Co

No Drawing Applicatio June, Im m 4 1,. Ser al 98 A 55 This invention relates to the flake formof catalyticallyactive compositions comprising" an irmrganie constituent dispersed in a' solidifiedoleaginous substance as a protective -mediur n andis-particularly concerned with the flake-form of hydrogenation" catalyst comprising" for example,- reduced nickel dispersed in a solidified oleaginous substance such as a solidified vegetable oil-as cottonseed oil, asa protective medium;

In'the hardening of oils, such as vegetable-oils, by; catalyticalhydrogenation, it 7 is customary to use a-catalyst comprising; for-example, reduced nickel; dispersed in an oil, usually a 'quantity'of the same oil which is to be cata-lytica'lly' hydrogenated' by theapplication of the nickel catalysti Ordinarily; the catalyst is prepared by reducinga nickel salt inthe oily theoi-lthen acting as a protective medium to prevent contact between the reduced nick eland-the air-andtherebyavoiding--oxidation ofthe'nickele It; has been customary---to-put-up such'catalytic material for shipmentby running-the hot liquid suspension of the reduced nickel dispersed in the Qil flom'" the reducers (at a temperature of about 350 F5) into steel drums of=fi fty g-allonscapacity and"per-niittin-g' the mixture to cool and splidi fm in the drums. Because of thi practice;- such product could be shipped solely in" steel drums.

Since-such -cat-alytic material -is sold on--thebasis of its reduced nickel content, a customary method of its determination has been to withdraw a sampleof -thet suspension shortlyi after the startof the run ot the suspension into the drum,' then to take a: secondsamplewhen the drum was about half tull an-d-tdtakea third sample when thedrum was about completely: full; and then to-putthe three samples together and -to melt .them-to:=-permit= their 1 intimate -mix-e tureandtoanalyze: the mixedsamplet. Theatre-esul-t was consideredto represent the-analysis:- of the drum; This procedure was repeated for each;

However, since these samples were takenstrom the: suspension while-it was in theliquid state-rand still veryhot; such analysis was: ofa no :benefit: to the customer in preparing to use the material in actual hydrogenation because rexperiencehas shownxthat the so1idified;.-1productisnot:homogeneous in compositionwthroughout. the-:drum.v This results from the fact: that l during: the: cooling: of the liquid-suspensionwhich ha \beent-run; into: the drum, the-heavy nickel: particleszltend; to settle to yarying extents w'ithin theoilsocthatzirr tile-finally solidifid 'composition; .thexnickel'; (3011:; tent varies throughout the: i-dru-m, inr-thatazit ace.

d sclaims. (01. 252-245) \1 1 tually increases with regularity from the: lowest n rsentese at h P' HhMW e h si ati heibeti m Cons quently; the user' or such catalytic composition; also experienced 'serious disadvantages with it; Eocheck the analysis of the productin the deli ereddrum, itwas necessary for thecustor'ner to-break open practically theentire drum and to chop outsamples from several points 'and to -melt -them-together for a-combined sample from-which the final analysis-wasmade: Then it-has'beenfound that atfthe plants in-preparing to 'use the material in hydrogenati'on the practice has necessarily been to chop outofthe drum an approximated amount ofthe suspension and to melt it andsample it for analysis tobe;ab1e to determin that a- "sumcient amount of catalytic nickel was being taken for the'; treatment of the particular batch of oil tube-hydrogenated; Therequisite amount of the catalytic composition could be added to the batch of oi-l to be hydrogenated only after thecomposition;wa vpreliininarily melted, or, in some cases; after it was-groundto afine state, otherwise proper mixture with the oil to be hydrogenatedwasnottobe'expectedi Also-inthisparticular-practice, further an-' noyance was experienced because the catalytic. composition was not-consistent in hardness and varied ii wide-the different: oleaginous substances,

such -as tl i'e variousvegetable: or animalfoi-ls-lused as protectivemedium: Forzeexample, when;v cottdnseedioil wasemployed" as; aprotective medium, the catalytic composition solidified toia. .very hard and brittle statee. With: coccanut ioil. mixturesas the inediume the; common; experience has: been that lthe' catalytic; composition, was rarely hard enough and eyen with; it; hardened to an extremelyrlow; iodine number; the: composition was stil11j'not quitehardzenough; When fish oil was used 'aspzazprotectivez medium, the finished: cats alytic composition-varied irom; .at times, a soft waxelikez. character; to; at other times, V a hard, brittleiype: Not, infrequently; the com: positiom'was foundrto be so; hard that thel'cus, tom'er::.ound it necessarysto-return the. material; to: theesupplier for the latter to chop up themass and grind it to a fine state. A

1 hesejipcons en s n heana end' t degree; oihardness;- oi the catalytically active, composition heretofore handled as a large; bulky; heaywusolid; mass; in steel drums or, for: example, fitty-reallons c pac ty; w thout em ha izi the, ar o having suc a vol me of the composition cooling from around:35 0"- F in-agon This invention presents a catalytically active composition, particularly a hydrogenation catalyzation composition, comprising a catalytically,

active inorganic constituent, especially such con-U stituent of metallic origin, and moreespecially,

for example, nickel in catalytically active statt e',"v

dispersed in a solidified oleaginous substanc'e' as" a protective medium, said composition .of the catalytically active constituent dispersed in the oil being in the form of flakes.

The'product of'the invention is prepared by running the hot suspension of the reduced nickel dispersed in theoil from the reducer to a cooling tank equipped with an agitator to keep the suspension in constant motion to maintain the homogeneity of its composition, and also equipped with heat exchange coils through which the temperature of the suspension is controlled at around 260? for example, from which tank the'uniform suspension is distributed along an element of the chilled rotating roll of a flaking machine, the rollbeing cooled, for example, with water at about 65 F., the solidified catalytic composition being removed from the roll and broken by a doctor along another element of the roll.

In general, the flake product of the invention is of fairly uniiorm thickness andof a substantially harden dwaxy nature and of uniform com posit pni t e, fla e odu on i ind vi u l tches be n g arlyv h i; c n

packed-in a y desir b e. packaaasflch a Pa e b x s, hard fibre ccnt neralba sl a d a, and ca bestq cd n su t e nsw h h e, perbottomsif desired. a H

e flakes w lyans ons uent v. a l w. considerable simplicity, ease and; convenience in h dling, not only .to the. manufacturer in storing and packaging the product, but also to the customer in storing and adding thecatalytic material to the batchof oil tobe hydrogenated The small size, of the-flakes permits ,theirydirect, addition and uniform distribution in thebatch and eliminates the previously necessary ,prea melting before addition to the batch. The homo: geneity in compositionlof the flakes presents to both' themanufacturer and customer uniform: analysis in any container and batch and avoids all the difficulty and annoyance heretofore expe-; rienced in determining the analysis after its production and in checking it by the customer and in arriving at the weight of the material to add to the batch. All that is necessary now is to work from the simply obtained analysis and Weigh out the amount of uniform composition fiakes'to give the total amount of nickel catalystrequiredfor the batch and to add this amount directlyto the batch. a *While the invention has been exemplified by describing it-more specifically with respect to the fiake composition comprising reduced nickel cat-- alyst dispersed in asolidified vegetableor animal oil, to which type of compositionit is unusually and particularly unexpectedly applicable, it need not be limited thereto." l 1 l p The catalytically active constituent dispersed in the protective medium may be another base metal of the iron group such as cobalt or iron, or a metal like copper, or a metal of the platinum group such as palladium or platinum, or in some modifications, a base metal such as chromium, manganesca molybdenum, titaniurngand vanadiumiiwhereveisuch metals-are to be applied as the hydrogenation catalyst in certain required conditions.

These metals, as also in the case of nickel, need not be employed solely in the form of th elemental metalin finely divided form, but may also. be;employed as the catalytically active constituent in. the form of their oxides, carbides, silicides and the like, or if desired as suitable v 7 Any form of the catalytic ingredientor constituent may be used alone or i admixturefiwith any other form of the same ingreof the catalytic composition may be dispersed in anysolidifiable oleaginous substance compatible.

client or of any form of any other suitable metal or metals which variations are intended in. the specification and the appending claim by the language catalytically active inorganic constituent{ and, specificallyas to nickel, b finickeIin catalytically active-state. When the catalyth cally active constituent is employed in th formof a suitable organic salt of any of the applicable.

metals, the: term finorgamc in the claims relates to the metallic element of such salt. 7

-I he inorganic catalytically active constituent with thematerial in'the hydrogenation of which the catalyst is to be used. Suchsuitable oleaginous substances are capableof hardening upon beingspread ina layer over a chilledsurface and of breaking into small fragments, after having f 'iiei gfor h rdencii u on; e l cm he l l m e-Les h nabc d c d: 1 Such solidifiable oleaginoussu-bstances mple m y e a v e b e. mamm hei ao hich. may b an i al re erred to csa niqil. f v eta :orie n j fiuita l respec ble ai s: a e e amp fied lbrfcotto s rt ut and rn'l nd: iker, vpm in ons, o the ta l i e ycsri i sni s ch t i -1. Th an m ti n .m yrb eriv d; from l dia imals onlna be ma l s ch: as fish; o l, Wh le iq and t e l ke- 1O he suitabl subs an es r may: e, s ear a :tallow ndethel k e lThesui a lelq eae nous s st ces.

of; the type; illustrated need, not ,';be used gsingly. They; may -he used-inany; convenient; combina ti 'ns'with one another, for example, nlixtures of cottonseed and'cocoanut oils'in varied proportions, OI'QCOQQflnutOi] with ;other suitable :oils or other combinationsgof;solidifiableoils.- j ,1;

.: *Whilelthei inventionhas been illustrated by dBr';

scribing certain embodiments thereof, ;it;is under,- stood that 7 suitable substitutioniiof; equivalents, modifications and variations may; be made: therein without departing from the spirit of the inventiom the scope of which is recited in the appending claims;..'.'.f j 1 if .i

j Thi liapplication; is; a continuationmof, my: 605 pending application Serial No; 295,333; fiiedgseptemberi-16,-.l939;' 7 :1; i; 'what is'claimedisnf The'inetho'd :of, preparingia; animate-j.

and mixtures thereof, which: method comprises continuously distributing a liquid suspension comprising said nickel in catalytically active state homogeneously dispersed in said oil in liquid state, over the rotating surface of a chilled drum to harden the composition and removing the hardened composition from said surface thereby breaking the hardened composition into flakes.

2. The method of preparing in solid form and in flakes a catalytically active composition having (as its essential constituents finely divided, catalytically active nickel, deleteriously effected by the air, uniformly homogeneously dispersed in, and protected against the deleterious effect of the air on its catalytic activity by, a solidifiable oil selected from the group consisting of vegetable oils, animal oils, and mixtures thereof, which method comprises keeping in motion a liquid suspension comprising said nickel in catalytically active state dispersed in said oil while in a melted and liquid state, tomaintain the uniform dispersion of the nickel in the suspension, continuously distributing a substantially uniformly thick layer of said suspension and of flake thickness over a chilled surface to congeal the composition while maintaining the uniform dispersion of the nickel in the solidifying oil, continuously moving freshly distributed suspension on the chilled surface relatively away from the station of distribution of it, and after keeping the cooling congealed suspension in contact with the chilled surface sufiiciently long to permit the composition to harden, separating the solidified, hardened composition from the chilled surface thereby causing the composition to break into substantially flat flakes having uniform thickness, due to the fragility of the hardened composition.

3. Readily flowing, uniformly homogeneous,

flat, uniformly thick, small flakes of a catalytically active composition containing as its essential ingredients finely divided, catalytically active nickel, ordinarily deleteriously effected by the air, uniformly dispersed in, and protected from the deleterious effect of the air on its catalytic activity by, a solidified oil selected from the group consisting of vegetable oils, animal oils, and mixtures thereof.

4. Readily flowing, uniformly homogeneous, flat, uniformly thick, small flakes of a catalytically active composition containing as its essential ingredients finely divided, catalytically active nickel, ordinarily deleteriously effected by the air, uniformly dispersed in, and protected against the deleterious effect of the air on its catalytic activity by, a solidified, marine animal oil.

MEYER L.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES I PATENTS Number Name Date 1,223,123 Sulzberger Apr. 17, 1917 2,084,687 Jesperson June 22, 1937 1,740,064 Boertlein Dec. 17, 1929 1,343,833 Leitch June 15, 1920 915,633 Strickler Mar. 16, 1909 1,594,390 Van Stone Aug. 3, 1926 1,911,479 Strosacker May 30, 1933 1,847,583 Williams Mar. 1, 1932 1,817,304 Foster Aug. 4, 1931 1,649,511 Cox Nov. 15, 1927 1,329,322 Ellis Jan, 27, 1920 

